Selectivity controlled synthesis of furan-ring nitrogenous compounds from 5-hydroxymethylfurfural, ammonia and hydrogen peroxide†

Nitrogenous compounds are significantly important in chemical and pharmaceutical applications. A series of furan-ring nitrogenous compounds were synthesized using 5-hydroxymethylfurfural (HMF). The ammoximation of HMF with ammonia, hydrogen peroxide, and the catalyst TS-1 realized the clean synthesis of 5-hydroxymethylfurfural oxime (HMFO), with a yield of 97.9% under suitable conditions. Based on this, a novel Cu(OAc)₂/TS-1 catalyst was prepared, and the solvent and reaction temperature were controlled for the selective synthesis of 5-hydroxymethyl-2-furancarbonitrile (HMFC) and 5-hydroxymethyl-2-furfuramide (HMFA) from HMFO. The yield of HMFC was 92.8% in the acetonitrile solvent at 60 °C, and the yield of HMFA was 90.7% in the isopropanol solvent at 95 °C. Cu(OAc)₂/TS-1 was very stable, with almost unchanged activity even after recycling it four times. This study provided an effective and intrinsically safe pathway for synthesizing bio-based high-value furan-ring nitrogenous compounds.